Method of producing polymer

ABSTRACT

A method of producing a polymer according to the present invention is characterized by comprising a step of photopolymerizing one or more photopolymerizable polymerization precursors by irradiation with an activation energy ray in a supercritical fluid or in a subcritical fluid.

This application is the U.S. National Phase under 35 U.S.C. §371 ofInternational Application PCT/JP03/16850, filed on Dec. 26, 2003, whichclaims priority of Japanese Patent Application No. 2003-047994, filed onFeb. 25, 2003. The International Application was published under PCTArticle 21(2) in a language other than English.

TECHNICAL FIELD

The present invention relates to a method of producing a polymer by theuse of a supercritical fluid or a subcritical fluid.

BACKGROUND ART

A supercritical fluid is a fluid having a density close to a liquid aswell as a viscosity and a diffusion coefficient close to a gas. Sincethe supercritical fluid possesses both of diffusivity of the gas andsubstance solubility of the liquid, it has various effects as a reactionsolvent.

Heretofore, the supercritical fluid has been utilized for extractiveseparation of effective ingredients and extractive removal ofunnecessary ingredients such as extraction of hop extracts and fragrantmaterials, and decaffeination from coffee and tobacco by the use of itsdissolving power. For example, caffeine-free coffee has beenindustrially manufactured by the utilization of supercritical carbondioxide since around last half of 1970s.

In recent years, the supercritical fluids have been utilized for removalof impurities from chemical materials, products and the like, andconcentration thereof, e.g., removal of unreacted monomers from apolymer, and concentration and dehydration of an alcohol. Furthermore,they have been also utilized for removal of a binder from ceramics,washing and drying of semiconductors and mechanical parts, and so forth.For example, Japanese Patent Application Laid-open No. 7-149721discloses a method for purifying a bismaleimide compound which ischaracterized by subjecting an ether imide-based bismaleimide compoundcontaining impurities such as aromatic hydrocarbon solvents used duringthe production of the same to an extractive removal treatment of theimpurities in which the compound is brought into contact with carbondioxide in a supercritical state or in a state close to thesupercritical state having a pressure of 60 atm or higher and atemperature of 20° C. or higher.

In addition to the above, the supercritical fluids have been utilizedfor the formation of fine particles, thin films and microfilaments byrapid expansion (RESS method), e.g., the production of whisker-like fineparticles of silica or the like. Moreover, they have been also utilizedfor the formation of fine particles and thin films by a conversiontechnique into a poor solvent (GAS method), e.g., strength enhancement(surface coating) of silica aerogel. For example, Japanese PatentApplication Laid-open No. 8-104830 discloses a production method of fineparticles for a paint wherein a polymer polymerization reaction solutionin a polymerization step for producing a polymeric solid material forthe paint is dissolved in a supercritical phase by the use of carbondioxide and a polar organic solvent, and then rapidly expanded.

Meanwhile, heretofore, polymers such as the fine particles for the painthave been produced by a solution polymerization method or the like usinga large amount of an organic solvent, in consideration of the control ofa polymerization reaction rate, the handling of the polymerized productand the like. However, in the solution polymerization method, thepolymer is formed in a solution state containing the solvent in abouthalf amount, and hence a solvent removing step is necessary where thesolvent is removed from the resulting polymer solution after thepolymerization and the polymer is then dried, which means that theprocess is troublesome. In addition, it is also troublesome to treat theorganic solvent which vaporizes in the solvent removing step.

Recently, it has been attempted to produce the polymer by the use of asupercritical fluid, particularly supercritical carbon dioxide as thesolvent. In the case of using supercritical carbon dioxide as thesolvent, the removal of the solvent after polymerization and the dryingare unnecessary, and therefore the process can be simplified and costscan be reduced. Moreover, since no organic solvent is used, a burden toenvironment is also slight. In addition, carbon dioxide can be easilyrecovered and re-used as compared with the organic solvent. Furthermore,in many cases, there is a difference in solubility in carbon dioxidebetween the polymer and monomers, so that amounts of the unreactedmonomers contained in the polymer which is the product are reduced byusing supercritical carbon dioxide as the solvent, to enable theproduction of the more highly pure polymer.

As a production method of a polymer by the use of the supercriticalfluid, for example, Japanese PCT Patent Application Laid-open No.7-505429 discloses a production method of a fluoro-polymer comprising astep of solubilizing a fluoro-monomer in a solvent comprisingsupercritical carbon dioxide, and a step of thermally polymerizing thefluoro-monomer in the solvent in the presence of a radicalpolymerization initiator to produce the fluoro-polymer.

Japanese Patent Application Laid-open No. 2000-26509 discloses aproduction method of a fluoro-polymer wherein at least one fluorinatedmonomer is thermally polymerized in supercritical carbon dioxide by theuse of dimethyl (2,2′-azobisisobutyrate) as a initiator.

Japanese Patent Application Laid-open No. 2002-327003 discloses aproduction method of a fluorinated alkyl group-containing polymer whichcomprises the step of thermally polymerizing a radical polymerizablemonomer component containing a fluorinated alkyl group-containing(meth)acrylate in an amount of 20% by weight or more by the use ofsupercritical carbon dioxide as a polymerization solvent.

Japanese Patent Application Laid-open No. 2001-151802 discloses aproduction method of polymer fine powder which comprises the step ofcarrying out thermal radical polymerization of a monomer compositioncontaining an ethylenically unsaturated monomer having a carboxyl groupsuch as (meth)acrylic acid in supercritical carbon dioxide to form thepolymer fine powder.

Japanese Patent Application Laid-open No. 2002-179707 discloses aproduction method of polymer fine particles which comprises the step ofcarrying out thermal polymerization of a monomer such as methylmethacrylate in supercritical carbon dioxide by the action of a radicalpolymerization initiator which is a polymer having a specific structuresubstantially soluble in supercritical carbon dioxide.

In addition, Japanese Patent Application Laid-open No. 2002-128808discloses a production method of a polymer which comprises the step ofcarrying out thermal radical polymerization of a polymerizable monomersuch as methyl methacrylate or styrene in supercritical carbon dioxidein the presence of a specific non-polymerizable dispersant such asdocosanoic acid or myristic acid.

Masanori Kobayashi et al., “Dispersion Polymerization of Vinyl MonomersUsing Supercritical Carbon Dioxide”, “Sikizai (Coloring Material)”,2002, Vol. 75, No. 8, p. 371–377 describes thatpoly(1,1,2,2-tetrahydroheptadecafluorodecyl acrylate) andpoly(1,1,2,2-tetrahydroheptadecafluorodecyl methacrylate) obtained by apolymerization reaction using supercritical carbon dioxide as a solventare used as surface active agents, and supercritical carbon dioxide isused as a solvent to carry out a dispersion polymerization of variousacrylic monomers.

As mentioned above, there has been already investigated the productionmethod of the polymer which comprises the step of carrying out thermalpolymerization of a monomer in a supercritical fluid such assupercritical carbon dioxide, but a production method of a polymer whichcomprises the step of photo-polymerizing a monomer in the supercriticalfluid is not known.

Meanwhile, in recent years, a polymer brush attracts attention owing toits unique morphology. The polymer brush has a structure where polymerchains, whose terminal is immobilized to a solid surface (by chemicalbond or adsorption), are stretched in the direction perpendicular to thesolid surface. The extent of the stretching of the polymer chainsnoticeably depends on a graft density.

The polymer brush is usually obtained by grafting polymer chains onto asolid surface by surface graft polymerization, especiallysurface-initiated living radical polymerization.

For example, Japanese Patent Application Laid-open No. 2001-131208discloses a production method of a polymer brush base material whichcomprises a step of providing a base material to which one or morefree-radical initiators each having a radical formation site at adistant position from the base material are covalently bonded, and astep of bringing the covalently-bonded base material into contact with amonomer under conditions for accelerating free-radical polymerizationfrom the radical formation sites of the initiators to form a polymerbrush.

Moreover, Japanese Patent Application Laid-open No. 2002-145971describes a production method of a polymer brush by surface-initiatedliving radical polymerization. Specifically, the surface-initiatedliving radical polymerization comprises a step of immobilizing apolymerization initiator onto a solid surface by the Langmuir-Blodgett(LB) method or a chemical adsorption method, and then a step of growinga polymer chain (graft chain) on the solid surface by living radicalpolymerization (ATRP method). Japanese Patent Application Laid-open No.2002-145971 describes that polymer chains having a regulated length andlength distribution can be grown on the surface of a base material withan unprecedentedly high surface density by the surface-initiated livingradical polymerization, and they are then swollen in a solvent owing tothe high graft density to provide a film thickness comparable to a fullystretched chain length and to thereby realize a “polymer brush” state ina true sense for the first time. Furthermore, Japanese PatentApplication Laid-open No. 2002-145971 describes that in the conventionalsurface-initiated radical polymerization, a radical once generatedcontinues to grow until its irreversible termination to form a graftchain sequentially and hence graft polymerization in the vicinity of thegraft chains previously grown is inhibited owing to the steric hindranceof the graft chains, but in the present system, polymerization proceedsin a living manner, that is, all the graft chains grow almost evenly andhence steric hindrance among neighboring graft chains is reduced, thefact being considered to be one cause of obtaining the high graftdensity.

In addition, Japanese Patent Application Laid-open No. 2002-145971mentioned above discloses a nano-structural functional material whereina chemical composition of a graft polymer chain constituting a graftpolymer layer arranged on a base material by graft polymerization isconverted into a multilayered structure in the film thickness directionby copolymerization with a different kind of a monomer or an oligomer,obtained by such surface-initiated living radical polymerization.Furthermore, Japanese Patent Application Laid-open No. 2002-145971mentioned above also discloses a nano-structural functional materialwherein a polymerization initiating portion (polymerization initiatinggroup) of a molecule arranged on the surface of a base material isinactivated with a predetermined pattern in the film surface directionand then the polymerization initiating portion not inactivated issubjected to graft polymerization to arrange a graft polymer layer witha predetermined pattern.

Furthermore, high density (dense) polymer brushes obtained bysurface-initiated living radical polymerization are described in detailin Takanobu Tsujii, “New Development of Polymer Brushes”, “Mirai Zairyou(Future Materials)”, Vol. 3, No. 2, p. 48–55.

In this connection, in these conventional polymer brushes, the polymerchains (graft chains) are possible to have a fully stretched structureonly in a good solvent, and the polymer chains (graft chains) has afallen structure or a folded structure in a dry state or in a poorsolvent.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a method of producing apolymer comprising a step of photopolymerizing a photopolymerizablepolymerization precursor (monomer etc.) in a supercritical fluid or in asubcritical fluid.

The invention relates to a method of producing a polymer comprising astep of photopolymerizing one or more photopolymerizable polymerizationprecursors by irradiation with an activation energy ray in asupercritical fluid or in a subcritical fluid.

Moreover, the invention relates to the above method, wherein the polymerto be produced is a film.

Furthermore, the invention relates to the above method, wherein apolymer film is formed on an activation energy ray-transmittable basematerial which is placed so as to be exposed to the supercritical fluidor subcritical fluid.

In addition, the invention relates to the above method, wherein one ormore photopolymerizable polymerization precursors are irradiated with anactivation energy ray through the activation energy ray-transmittablebase material which is placed so that a surface thereof through whichthe activation energy ray is incident is not exposed to thesupercritical fluid or subcritical fluid and another surface thereofthrough which the activation energy ray is outgoing is exposed to thesupercritical fluid or subcritical fluid, to photopolymerize the one ormore polymerization precursors, whereby the polymer film is formed onthe activation energy ray outgoing surface of the activation energyray-transmittable base material.

Moreover, the invention relates to the above method, wherein theactivation energy ray-transmittable base material is irradiated with theactivation energy ray through a mask pattern to selectively form thepolymer film on an activation energy ray-transmitted part of theactivation energy ray outgoing surface of the activation energyray-transmittable base material.

Furthermore, the invention relates to the above method, wherein thepolymer to be produced is a polymer containing a furry protrusion.

Moreover, the invention relates to the above method, wherein the polymercontaining the furry protrusion is formed on the activation energyray-transmittable base material which is placed so as to be exposed tothe supercritical fluid or subcritical fluid.

Furthermore, the invention relates to the above method, wherein one ormore photopolymerizable polymerization precursors are irradiated with anactivation energy ray through the activation energy ray-transmittablebase material which is placed so that a surface thereof through whichthe activation energy ray is incident is not exposed to thesupercritical fluid or subcritical fluid and another surface thereofthrough which the activation energy ray is outgoing is exposed to thesupercritical fluid or subcritical fluid, to photopolymerize the one ormore polymerization precursors, whereby the polymer containing the furryprotrusion is formed on the activation energy ray outgoing surface ofthe activation energy ray-transmittable base material.

In addition, the invention relates to the above method, wherein theactivation energy ray-transmittable base material is irradiated with theactivation energy ray through a mask pattern to selectively form thepolymer containing the furry protrusion on an activation energyray-transmitted part of the activation energy ray outgoing surface ofthe activation energy ray-transmittable base material.

Herein, “a polymer containing a furry protrusion” means a protrudingpolymer or a polymer having one or more furry protrusions. In the caseof the protruding polymer, the polymer itself is called a “furryprotrusion”, while in the case of the polymer having one or more furryprotrusions, the furry protrusion is called a “furry protrusion”. The“polymer containing the furry protrusion” includes a so-called polymerbrush, but is not limited thereto.

Moreover, in the case that the diameter of the furry protrusion (lengthof the furry protrusion in the direction parallel to the surface of thebase material) is not constant, the longest diameter (major axis ormajor side) at the bottom of the furry protrusion is determined as thediameter.

Furthermore, “a polymer film” includes porous one.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic constitutional drawing of one example ofproduction apparatus for carrying out the method of producing thepolymer of the present invention.

FIG. 2 is a SEM photograph of the polymer containing the furryprotrusion obtained in Example 6.

FIG. 3 is a SEM photograph of the polymer containing the furryprotrusion obtained in Example 7.

FIG. 4 is a SEM photograph of the polymer containing the furryprotrusion obtained in Example 8.

FIG. 5 is a SEM photograph of the polymer film obtained in Example 9.

FIG. 6 is a pattern sectional view of the polymer film obtained inExample 9.

DESCRIPTION OF THE MAIN SYMBOLS

-   1 Carbon dioxide cylinder-   2 Pump for carbon dioxide supply-   3 Reactor-   4 Temperature-controlling means-   5 Window-   5′ Window-   6 Light source-   7 Pressure-reducing valve-   8 Activation energy ray-transmittable base material-   9 Magnetic stirrer-   10 Stirring bar-   11 Base material-   12 Polymer film

BEST MODE FOR CARRYING OUT THE INVENTION

According to the invention, a photopolymerizable polymerizationprecursor (hereinafter, also referred to as “polymerization precursor”)is photopolymerized in a supercritical fluid or in a subcritical fluid,whereby a polymer can be produced.

Moreover, according to the invention, the polymerization precursor isphotopolymerized in the supercritical fluid or in the subcritical fluid,whereby a polymer film can be formed on a base material. Furthermore,the polymer film can be selectively formed on the activation energyray-transmitted part of the activation energy ray outgoing surface ofthe base material by irradiation of the base material with an activationenergy ray through a mask pattern and transmitting the ray. That is, apolymer film having a desired fine pattern can be formed on the basematerial.

In addition, according to the invention, the polymerization precursor isphotopolymerized in the supercritical fluid or in the subcritical fluid,whereby a polymer containing a furry protrusion can be formed on thebase material. Furthermore, the polymer containing the furry protrusioncan be selectively formed on the activation energy ray-transmitted partof the activation energy ray outgoing surface of the base material byirradiation of the base material with the activation energy ray througha mask pattern and transmitting the ray. That is, a polymer containing afurry protrusion having a desired fine pattern can be formed on the basematerial.

The following will describe the invention in detail.

In the invention, a supercritical fluid or a subcritical fluid is usedas a polymerization solvent.

The supercritical fluid means a fluid in a state where both oftemperature and pressure exceed their critical points, i.e., in a stateof a temperature equal to or higher than the critical temperature and apressure equal to or higher than the critical pressure. The criticaltemperature and the critical pressure are values inherent in asubstance. For example, the critical temperature and critical pressureof carbon dioxide are 30.9° C. and 7.38 MPa, respectively. The criticaltemperature and critical pressure of methanol are 239.4° C. and 8.09MPa, respectively. The critical temperature and critical pressure ofwater are 374.1° C. and 22.12 MPa, respectively.

Moreover, the subcritical fluid is a fluid which exhibits operations andeffects similar to the case of supercritical fluid, and is usually afluid having a temperature of 0.65 time as much as the criticaltemperature by the Kelvin scale or higher and a pressure of 0.65 time asmuch as the critical pressure or higher.

The supercritical fluid or subcritical fluid may be suitably selecteddepending on the solubility of the polymerization precursor and thelike. Examples of the supercritical fluid or subcritical fluid includecarbon dioxide, water, methane, ethane, ethylene, propane, propylene,alcohols such as methanol, ammonia, chlorofluorocarbon, carbon monoxide,and the like, and also inorganic gases such as nitrogen, helium, andargon. The supercritical fluid or subcritical fluid can be a mixture oftwo or more of them.

In the invention, the supercritical fluid or subcritical fluid ispreferably supercritical carbon dioxide or subcritical carbon dioxidesince a supercritical state or a subcritical state is achieved at arelatively low temperature under a relatively low pressure.

The using amount of the supercritical fluid or subcritical fluid may besuitably determined depending on the polymerization precursor, reactionconditions and the like. For example, the charging concentration of thepolymerization precursor can be about 1% by weight to about 70% byweight.

In the invention, the supercritical fluid or subcritical fluid is usedas a reaction field but the other liquid or gas may be present therein.

In the invention, for the purpose of increasing the concentration of thepolymerization precursor or photopolymerization initiator in thesupercritical fluid phase or in the subcritical fluid phase, aco-solvent (entrainer) which assists to dissolve the solutes, i.e., thepolymerization precursor or photopolymerization initiator may be used.

The entrainer can be suitably selected depending on the supercriticalfluid or subcritical fluid and the polymerization precursor to be used,and the like.

In the case of using supercritical carbon dioxide or subcritical carbondioxide, examples of the entrainer include methanol, ethanol, propane,butane, hexane, octane, acetic acid, ethyl acetate, acetone, water,acetonitrile, dichloromethane, and the like. The entrainer may be usedsingly or as a mixture of two or more of them.

The using amount of the entrainer can be suitably determined.

The pressure at the polymerization reaction (polymerization pressure)can be suitably determined depending on the supercritical fluid orsubcritical fluid and the polymerization precursor, properties of theaimed polymer, and the like. The polymerization pressure is preferably0.65 time as much as the critical pressure of the fluid or higher, morepreferably equal to or more than the critical pressure. In the case ofusing supercritical carbon dioxide or subcritical carbon dioxide, thepolymerization pressure is preferably 5 MPa or higher, more preferably 7MPa or higher, particularly preferably the critical pressure, i.e., 7.4MPa or higher. When the polymerization pressure is within this range,the polymerization reaction proceeds more favorably and a polymer havinga higher quality is obtained. The upper limit of the polymerizationpressure is not particularly limited, but can be usually set at apressure in the range of 150 MPa or lower in terms of pressure tightnessof apparatus.

The polymerization pressure may be maintained at a constant pressurefrom the start of the polymerization until the completion, or thepressure may be changed during the polymerization, e.g., the pressuremay be elevated or reduced with the progress of the polymerization.

Moreover, the temperature at the polymerization reaction (polymerizationtemperature) can be suitably determined depending on the supercriticalfluid or subcritical fluid and the polymerization precursor, propertiesof the aimed polymer, and the like. The polymerization temperature ispreferably 0.65 time as much as the critical temperature of the fluid orhigher, more preferably equal to or more than the critical temperature.In the case of using supercritical carbon dioxide or subcritical carbondioxide, the polymerization temperature is preferably 20° C. or higher,more preferably 30° C. or higher, particularly preferably the criticaltemperature, i.e., 31° C. or higher. When the polymerization temperatureis within this range, the polymerization reaction proceeds morefavorably and a polymer having a higher quality is obtained. The upperlimit of the polymerization temperature is not particularly limited, butcan be usually set at a temperature in the range of 250° C. or lower.

The polymerization temperature may be maintained at a constanttemperature from the start of the polymerization until the completion,or the temperature may be changed during the polymerization.

With regard to the supercritical fluid or subcritical fluid, the densityand polarity thereof can be changed by the pressure or temperature, andthereby the solubility of the polymerization precursor in the solvent(the supercritical fluid or subcritical fluid) can be varied. Therefore,in the case that two or more polymerization precursors are polymerized,the composition of the resulting polymer can be controlled bycontrolling the polymerization pressure and polymerization temperature.Furthermore, it is also possible to change the composition of theresulting polymer, for example, in the direction of the film thicknessor in the direction perpendicular to the base material by changing atleast either of the pressure or the temperature during thepolymerization.

In the invention, in the supercritical fluid or subcritical fluid asmentioned above, one or more polymerization precursors arephotopolymerized by irradiation with an activation energy ray in thepresence of a photopolymerization initiator, if necessary.

The activation energy ray for the irradiation can be suitably determineddepending on the polymerization precursor, the photopolymerizationinitiator and the like. As the activation energy ray, an ultraviolet rayhaving a wavelength of 10 to 380 nm, a visible light ray having awavelength of 380 to 780 nm, a near-infrared ray having a wavelength of780 nm (0.78 μm) to 2.5 μm, and the like are mentioned. In many cases,as the activation energy ray, an ultraviolet ray or visible light rayhaving a wavelength of 500 nm or shorter, more preferably an ultravioletray or visible light ray having a wavelength of 420 nm or shorter,particularly an ultraviolet ray having a wavelength of 380 nm orshorter, furthermore an ultraviolet ray having a wavelength of 330 nm orshorter is employed.

In this connection, the activation energy ray for the irradiation maynot be a ray having a single wavelength or a ray having a single peak inspectral distribution, and may have any spectral distribution as far asthe ray contains a light having the above wavelength.

As lamps (light sources) for use in the irradiation with the activationenergy ray, any of the lamps generally employed can be used, andexamples thereof include an ultrahigh pressure mercury lamp, a highpressure mercury lamp, a medium pressure mercury lamp, a low pressuremercury lamp, a chemical lamp, a metal halide lamp, a carbon arc lamp, axenon lamp, a mercury-xenon lamp, a tungsten lamp, a hydrogen lamp, adeuterium lamp, an excimer lamp, a short arc lamp, a laser having anoscillation ray at UV laser (wavelength: 351 nm to 364 nm), ahelium-cadmium laser, an argon laser, an excimer laser, and the like.

The dose (integrating amount of light) of the activation energy ray canbe suitably determined depending on the desired polymerization degree ofthe polymer, the desired film thickness of the polymer film, the desiredheight of the furry protrusion of the polymer containing the furryprotrusion, and the like. The dose of the activation energy ray may be,for example, 0.5 mJ/cm² to 100 J/cm², more preferably 1 mJ/cm² or moreand 10 J/cm² or less.

In this connection, the dose of the activation energy ray is defined bythe following equation:Dose of activation energy ray (J/cm²)=Intensity of activation energy ray(W/Cm²)×Irradiation time (sec).

The dose of the activation energy ray can be controlled by irradiationtime, lamp power and the like.

The intensity of the activation energy ray can be suitably determinedand can be, for example, 0.01 mW/cm² to 1 teraW/cm² (TW/cm²). Moreover,the irradiation time of the activation energy ray may be determined sothat a desired dose can be obtained according to the intensity of theactivation energy ray.

In the invention, photopolymerization can be carried out by dissolvingand dispersing a polymerization precursor and a nano particle (anultra-fine particle having an average particle size of, for example, 100nm or less) preferably homogeneously in a supercritical fluid or in asubcritical fluid, and then irradiating the whole with an activationenergy ray. Examples of the nano particles include nano carbon, CdSe,and the like. Thereby, a polymer or a polymer film (including a polymercontaining a furry protrusion) wherein the nano particles arehomogeneously dispersed can be formed. If necessary, the other additivescan be added.

The polymerization precursor to be applied to the invention is notparticularly limited as far as it dissolves in the solvent, i.e., thesupercritical fluid or subcritical fluid and has photopolymerizability.The polymerization precursor can be polymerized in a state where partthereof is dissolved in the supercritical fluid or subcritical fluid. Inaddition, the polymerization precursor may be a monomer, an oligomer, ora polymer.

Examples of the polymerization precursor include compounds having one ormore structures selected from the group consisting of a maleimide groupoptionally having a substituent, a (meth)acryloyl group optionallyhaving a substituent, a cyclic ether structure optionally having asubstituent, an alkenyl group optionally having a substituent, avinylene group optionally having a substituent, a styryl groupoptionally having a substituent, and an azido group. Herein, the(meth)acryloyl group means an acryloyl group and a methacryloyl group.In the case that the polymerization precursor has two or more of thesegroups, the polymerization precursor may have only the same group or mayhave different groups. In this connection, the substituent is notparticularly limited as far as it does not inhibit the polymerizationreaction, and examples thereof include hydrocarbon groups having 12carbon atoms or less, halogen atoms, an amino group, a carboxyl group, ahydroxyl group, a cyano group, and the like.

As the polymerization precursor, preferred is a spontaneouslyphotopolymerizable compound which is a compound photopolymerizable inthe absence of a photopolymerization initiator.

As the polymerization precursor which is a spontaneouslyphotopolymerizable compound, there is mentioned, for example, amaleimide-based compound having at least one maleimide group at theterminal, specifically a maleimide-based compound represented by thefollowing general formula (1):

wherein A represents a hydrocarbon group optionally having asubstituent, or a (poly)ether connecting chain or a (poly)ether residue,(poly)ester connecting chain or a (poly)ester residue, (poly)urethaneconnecting chain or a (poly)urethane residue, or a (poly)carbonateconnecting chain or (poly)carbonate residue having a molecular weight of40 to 100,000 to which a hydrocarbon group optionally having asubstituent is bonded via at least one bond selected from the groupconsisting of an ether bond, an ester bond, a urethane bond, and acarbonate bond; B represents an ether bond, an ester bond, a urethanebond, or a carbonate bond; R represents a hydrocarbon group optionallyhaving a substituent; and m represents an integer of 1 to 6; providedthat all of B or R are not necessarily the same and two or more kinds ofB or R may be present when m is an integer of 2 or larger.

In view of forming a cured film by itself, m in the general formula (1)is preferably an integer of 2 to 6.

R in the general formula (1) is preferably an alkylene group, acycloalkylene group, an arylalkylene group, or a cycloalkylalkylenegroup. The alkylene group herein may be a linear one or a branched one.The arylalkylene group or cycloalkylalkylene group may have an arylgroup or a cycloalkyl group in the main chain or may have an aryl groupor a cycloalkyl group in the branched chain. In view of curability, R ispreferably a linear alkylene group having 1 to 5 carbon atoms or abranched alkylene group having 1 to 5 carbon atoms.

Specific examples of R in the general formula (1) include linearalkylene groups such as a methylene group, an ethylene group, atrimethylene group, a tetramethylene group, a pentamethylene group, ahexamethylene group, a heptamethylene group, an octamethylene group, anonamethylene group, a decamethylene group, an undecamethylene group,and a dodecamethylene group; branched alkylene groups such as a1-methylethylene group, a 1-methyl-trimethylene group, a2-methyl-trimethylene group, a 1-methyl-tetramethylene group, a2-methyl-tetramethylene group, a 1-methyl-pentamethylene group, a2-methyl-pentamethylene group, a 3-methyl-pentamethylene group, and aneopentyl group; cycloalkylene groups such as a cyclopentylene group anda cyclohexylene group; arylalkylene groups having an aryl group in themain chain or the side chain, such as a benzylene group, a2,2-diphenyl-trimethylene group, 1-phenyl-ethylene group,1-phenyl-tetraethylene group, and 2-phenyl-tetraethylene group;cycloalkyl-alkylene groups having a cycloalkyl group in the main chainor the side chain, such as a cyclohexylmethylene group, a1-cyclohexyl-ethylene group, a 1-cyclohexyl-tetraethylene group, and a2-cyclohexyl-tetraethylene group; and the like.

A in the general formula (1) represents a hydrocarbon group optionallyhaving a substituent, or a (poly)ether connecting chain or a (poly)etherresidue (A-1), (poly)ester connecting chain or a (poly)ester residue(A-2), (poly)urethane connecting chain or a (poly)urethane residue(A-3), or a (poly)carbonate connecting chain or (poly)carbonate residue(A-4) having a molecular weight of 40 to 100,000 to which a hydrocarbongroup optionally having a substituent is bonded via at least one bondselected from the group consisting of an ether bond, an ester bond, aurethane bond, and a carbonate bond. A may be a connecting chainconstituted by an oligomer or polymer wherein these connecting chainsare repeated as one repeating unit.

Specific examples of A in the general formula (1) include thehydrocarbon groups mentioned as specific examples of R.

In addition, as A in the general formula (1), there are mentioned aconnecting chain or a residue (A-1) constituted by a (poly)ether(poly)olhaving a molecular weight of 40 to 100,000 and having one unit orrepeating units in which at least one hydrocarbon group selected fromthe group consisting of a linear alkylene group, a branched alkylenegroup, a cycloalkylene group, and an aryl group is bonded via an etherbond; a connecting chain or residue (A-2-1) constituted by a(poly)ester(poly)ol having a molecular weight of 40 to 100,000 andhaving one unit or repeating units in which at least one hydrocarbongroup selected from the group consisting of a linear alkylene group, abranched alkylene group, a cycloalkylene group, and an aryl group isbonded via an ester bond; a connecting chain or residue (A-2-2)constituted by a (poly)carboxylic acid{(poly)ether(poly)ol}ester havinga polycarboxylic acid residue in the terminal, obtainable by esterifyinga (poly)ether(poly)ol having a molecular weight of 40 to 100,000 andhaving one unit or repeating units in which at least one hydrocarbongroup selected from the group consisting of a linear alkylene group, abranched alkylene group, a cycloalkylene group, and an aryl group isbonded via an ether bond, with a di-, tri-, penta-, or hexa-carboxylicacid (hereinafter, abbreviated as polycarboxylic acid); a connectingchain or residue (A-2-3) constituted by a (poly)carboxylicacid{(poly)ester(poly)ol}ester having a polycarboxylic acid residue inthe terminal, obtainable by esterifying a (poly)ester(poly)ol having amolecular weight of 40 to 100,000 and having one unit or repeating unitsin which at least one hydrocarbon group selected from the groupconsisting of a linear alkylene group, a branched alkylene group, acycloalkylene group, and an aryl group is bonded via an ether bond andan ester bond, with a polycarboxylic acid; a connecting chain or residue(A-5) obtainable by ring-opening a (poly)epoxide having a molecularweight of 100 to 40,000 and having one unit or repeating units in whichat least one hydrocarbon group selected from the group consisting of alinear alkylene group, a branched alkylene group, a cycloalkylene group,and an aryl group is bonded via an ether bond; a connecting chain orresidue (A-3-1) constituted by a (poly)ether(poly)isocyanate obtainableby urethane formation of a (poly)ether(poly)ol having a molecular weightof 40 to 100,000 and having one unit or repeating units in which atleast one hydrocarbon group selected from the group consisting of alinear alkylene group, a branched alkylene group, a cycloalkylene group,and an aryl group is bonded via an ether bond, with an organic(poly)isocyanate; a connecting chain or residue (A-3-2) constituted by a(poly)ester(poly)isocyanate obtainable by urethane formation of a(poly)ester(poly)ol having a molecular weight of 40 to 100,000 andhaving one unit or repeating units in which at least one hydrocarbongroup selected from the group consisting of a linear alkylene group, abranched alkylene group, a cycloalkylene group, and an aryl group isbonded via an ester bond, with an organic (poly)isocyanate; a connectingchain or residue (A-4) constituted by a carbonic acid ester of a(poly)ether(poly)ol having a molecular weight of 40 to 100,000 andhaving one unit or repeating units in which at least one hydrocarbongroup selected from the group consisting of a linear alkylene group, abranched alkylene group, a cycloalkylene group, and an aryl group isbonded via an ether bond; and the like. In this connection, (A-2-1),(A-2-2), and (A-2-3) are included in the (poly)ester connecting chain or(poly)ester residue (A-2) in the general formula (1). Also, (A-3-1) and(A-3-2) are included in the (poly)urethane connecting chain or(poly)urethane residue (A-3) in the general formula (1).

Examples of the (poly)ether(poly)ol constituting the above connectingchain or residue (A-1) include polyalkylene glycols such as polyethyleneglycol, polypropylene glycol, polybutylene glycol, andpolytetramethylene glycol; and ethylene oxide-modified products,propylene oxide-modified products, butylene oxide-modified products, andtetrahydrofuran-modified products of alkylene glycols such as ethyleneglycol, propanediol, propylene glycol, tetramethylene glycol,pentamethylene glycol, hexanediol, neopentyl glycol, glycerin,trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane,and dipentaerythritol. Of these, various modified products of alkyleneglycols are preferred. Furthermore, the (poly)ether(poly)ol constitutingthe above connecting chain or residue (A-1) include copolymers ofethylene oxide and propylene oxide, copolymers of propylene glycol andtetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran,hydrocarbon-based polyols such as polyisoprene glycol, hydrogenatedpolyisoprene glycol, polybutadiene glycol, and hydrogenatedpolybutadiene glycol, polyhydric hydroxyl compounds such aspolytetramethylene hexaglyceryl ether (tetrahydrofuran-modified productsof hexaglycerin), and the like.

Examples of the (poly)ester(poly)ol constituting the above connectingchain or residue (A-2-1) include ε-caprolactone-modified products,γ-butyrolactone-modified products, δ-valerolactone-modified products, ormethylvalerolactone-modified products of polyalkylene glycols such aspolyethylene glycol, polypropylene glycol, polybutylene glycol, andpolytetramethylene glycol or alkylene glycols such as ethylene glycol,propanediol, propylene glycol, tetramethylene glycol, pentamethyleneglycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane,pentaerythritol, diglycerin, ditrimethylolpropane, anddipentaerythritol; aliphatic polyesterpolyols which are esterificationproducts of aliphatic dicarboxylic acids such as adipic acid and dimeracid with polyols such as neopentyl glycol and methylpentanediol;polyesterpolyols such as aromatic polyesterpolyols which areesterification products of aromatic dicarboxylic acids such asterephthalic acid with polyols such as neopentyl glycol; esterificationproducts of polyhydric hydroxyl compounds such as polycarbonate polyols,acryl polyols, polytetramethylene hexaglyceryl ether(tetrahydrofuran-modified product of hexaglycerin) with dicarboxylicacids such as fumaric acid, phthalic acid, isophthalic acid, itaconicacid, adipic acid, sebacic acid, and maleic acid; polyhydric hydroxylcompounds such as monoglycerides obtainable by ester-exchange reactionof polyhydric hydroxyl compounds such as glycerin with fatty acidesters; and the like.

Examples of the (poly)carboxylic acid{(poly)ether(poly)ol}esterconstituting the above connecting chain or residue (A-2-2) and having apolycarboxylic acid in the terminal include (poly)carboxylicacid{(poly)ether(poly)ol}esters having a polycarboxylic acid in theterminal, which are obtainable by esterification of polycarboxylic acidssuch as succinic acid, adipic acid, phthalic acid, hexahydrophthalicacid, tetrahydrophthalic acid, fumaric acid, isophthalic acid, itaconicacid, adipic acid, sebacic acid, maleic acid, trimellitic acid,pyromellitic acid, benzenepentacarboxylic acid, benzenehexacarboxylicacid, citric acid, tetrahydrofurantetracarboxylic acid, andcyclohexanetricarboxylic acid with the (poly)ether(poly)ols shown in theabove (A-1), and the like.

Examples of the (poly)carboxylic acid{(poly)ester(poly)ol}esterconstituting the above connecting chain or residue (A-2-3) and having apolycarboxylic acid in the terminal include (poly)carboxylicacid{(poly)ester(poly)ol}esters having a polycarboxylic acid in theterminal, which are obtainable by esterification of di-, tri-, penta-,and hexa-carboxylic acids such as succinic acid, adipic acid, phthalicacid, hexahydrophthalic acid, tetrahydrophthalic acid, fumaric acid,isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid,trimellitic acid, pyromellitic acid, benzenepentacarboxylic acid,benzenehexacarboxylic acid, citric acid, tetrahydrofurantetracarboxylicacid, and cyclohexanetricarboxylic acid with the (poly)ester(poly)olsshown in the above (A-2).

Examples of the (poly)epoxide constituting the above connecting chain orresidue (A-5) include epichlorohydrin-modified bisphenol-type epoxyresins synthesized from (methyl)epichlorohydrin and bisphenol A,bisphenol F, their ethylene oxide-modified products and propyleneoxide-modified products, or the like; epichlorohydrin-modifiedhydrogenated bisphenol-type epoxy resins and epoxy novolak resinssynthesized from (methyl)epichlorohydrin and hydrogenated bisphenol A,hydrogenated bisphenol F, their ethylene oxide-modified products andpropylene oxide-modified products, or the like; reaction products ofphenol, biphenol, and the like with (methyl)epichlorohydrin; aromaticepoxy resins such as glycidyl esters of terephthalic acid, isophthalicacid, or pyromellitic acid; polyglycidyl ethers of glycols such as(poly)ethylene glycol, (poly)propylene glycol, (poly)butylene glycol,(poly)tetramethylene glycol, and neopentyl glycol and their alkyleneoxide-modified products; glycidyl ethers of aliphatic polyhydricalcohols such as trimethylolpropane, trimethylolethane, glycerin,diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, and1,6-hexanediol and their alkylene oxide-modified products; glycidylesters of carboxylic acids such as adipic acid, sebacic acid, maleicacid, and itaconic acid; glycidyl ethers of polyesterpolyols ofpolyhydric alcohols with polyhydric acids; copolymers of glycidyl(meth)acrylate or methylglycidyl (meth)acrylate; glycidyl esters ofhigher fatty acids, aliphatic epoxy resins such as epoxidized linseedoil, epoxidized soybean oil, epoxidized ricinus oil, and epoxidizedpolybutadiene; and the like.

Examples of the (poly)ether(poly)isocyanate constituting the aboveconnecting chain or residue (A-3) include (poly)ether(poly)isocyanatesobtainable by urethane-forming reaction of (poly)ether(poly)ols withpolyisocyanates, e.g., aliphatic diisocyanate compounds such asmethylene diisocyanate, hexamethylene diisocyanate,trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, lysinediisocyanate, dimer acid diisocyanate; aromatic diisocyanate compoundssuch as 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylenediisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthylenediisocyanate, and 3,3′-dimethylbiphenyl-4,4′-diisocyanate; alicyclicdiisocyanates such as isophorone diisocyanate,4,4′-methylenebis(cyclohexyl isocyanate),methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate,and 1,3-(isocyanatomethylene)cyclohexane; and the like.

Examples of the (poly)ether(poly)ol for use in the reaction with thepolyisocyanates include polyalkylene glycols such as polyethyleneglycol, polypropylene glycol, polybutylene glycol, andpolytetramethylene glycol; and ethylene oxide-modified products,propylene oxide-modified products, butylene oxide-modified products, andtetrahydrofuran-modified products of alkylene glycols such as ethyleneglycol, propanediol, propylene glycol, tetramethylene glycol,pentamethylene glycol, hexanediol, neopentyl glycol, glycerin,trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane,dipentaerythritol, and the like. Of these, various modified products ofalkylene glycols are preferred. Furthermore, the (poly)ether(poly)olsfor use in the reaction with the polyisocyanates include copolymers ofethylene oxide and propylene oxide, copolymers of propylene glycol andtetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran,hydrocarbon-based polyols such as polyisoprene glycol, hydrogenatedpolyisoprene glycol, polybutadiene glycol, and hydrogenatedpolybutadiene glycol; polyhydric hydroxyl compounds such aspolytetramethylene hexaglyceryl ether (tetrahydrofuran-modified productsof hexaglycerin), and the like.

Examples of the (poly)ester(poly)isocyanate constituting the aboveconnecting chain or residue (A-3-1) include (poly)ester(poly)isocyanatesobtainable by urethane-formation of the polyisocyanates mentioned in theconnecting chain or residue (A-1) with (poly)ester(poly)ols, and thelike.

Examples of the (poly)ester(poly)ol for use in the reaction with thepolyisocyanates include ε-caprolactone-modified products,γ-butyrolactone-modified products, δ-valerolactone-modified products, ormethylvalerolactone-modified products of alkylene glycols such asethylene glycol, propanediol, propylene glycol, tetramethylene glycol,pentamethylene glycol, hexanediol, neopentyl glycol, glycerin,trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane,and dipentaerythritol; aliphatic polyesterpolyols which areesterification products of aliphatic dicarboxylic acids such as adipicacid and dimer acid with polyols such as neopentyl glycol andmethylpentanediol; polyesterpolyols such as aromatic polyesterpolyolswhich are esterification products of aromatic dicarboxylic acids such asterephthalic acid with polyols such as neopentyl glycol; esterificationproducts of polyhydric hydroxyl compounds such as polycarbonate polyols,acryl polyols, polytetramethylene hexaglyceryl ether(tetrahydrofuran-modified product of hexaglycerin) with dicarboxylicacids such as fumaric acid, phthalic acid, isophthalic acid, itaconicacid, adipic acid, sebacic acid, and maleic acid; polyhydric hydroxylcompounds such as monoglycerides obtainable by ester-exchange reactionof polyhydric hydroxyl compounds such as glycerin with aliphatic esters;and the like.

Examples of the (poly)ether(poly)ol constituting the above connectingchain or residue (A-4) include (poly)ether(poly)ols mentioned in theconnecting chain or residue (A-1), and the like.

As compounds for use in carbonic acid ester formation with the(poly)ether(poly)ols, diethyl carbonate, dipropyl carbonate, phosgene,and the like may be mentioned. Also, polycarbonate can be formed byalternating copolymerization of an epoxide with carbon dioxide.

Of these, A in the general formula (1) is preferably a (poly)etherconnecting chain or (poly)ether residue (A-1) or a (poly)esterconnecting chain or (poly)ester residue (A-2) having a molecular weightof 100 to 100,000 wherein at least one group selected from the groupconsisting of a linear alkylene group having 2 to 24 carbon atoms, abranched alkylene group having 2 to 24 carbon atoms, a hydroxylgroup-containing alkylene group having 2 to 24 carbon atoms,cycloalkylene group, an aryl group, and an arylalkylene group is bondedvia at least one bond selected from the group consisting of an etherbond and an ester bond, more preferably a (poly)ether connecting chainor (poly)ether residue (A-1) having a molecular weight of 100 to 100,000which comprises repeating units containing a linear alkylene grouphaving 2 to 24 carbon atoms, a branched alkylene group having 2 to 24carbon atoms, a hydroxyl group-containing alkylene group having 2 to 24carbon atoms and/or an aryl group, and a (poly)ester connecting chain or(poly)ester residue (A-2) having a molecular weight of 100 to 100,000which comprises repeating units containing a linear alkylene grouphaving 2 to 24 carbon atoms, a branched alkylene group having 2 to 24carbon atoms, a hydroxyl group-containing alkylene group having 2 to 24carbon atoms and/or an aryl group.

In view of curability, the maleimide-based compound represented by theabove general formula (1) is preferably a maleimide-based compoundwherein R is an alkylene group having 1 to 5 carbon atoms, B is an esterbond represented by —COO— or —OCO—, A is a (poly)ether connecting chainor (poly)ether residue (A-1) having a molecular weight of 100 to 1,000which comprises repeating units containing a linear alkylene grouphaving 2 to 6 carbon atoms, a branched alkylene group having 2 to 6carbon atoms, or a hydroxyl group-containing alkylene group having 2 to6 carbon atoms.

As such a maleimide-based compound, a polyether bismaleimide acetaterepresented by the following general formula (2):

wherein R¹ represents an alkylene group and n is an integer of 1 to1,000, may be mentioned, for example.

The maleimide-based compound represented by the above general formula(1) can be synthesized, for example, by a known method from a maleimidecompound having a carboxyl group and a compound reactive to the carboxylgroup. Examples of the compound reactive to the carboxyl group includebifunctional to hexafunctional polyols or polyepoxides having an averagemolecular weight of 100 to 1,000,000 and having one unit or repeatingunits in which at least one hydrocarbon group selected from the groupconsisting of a linear alkylene group, a branched alkylene group, acycloalkylene group, and an aryl group is bonded via an ether bondand/or an ester bond, and the like.

Also, the maleimide-based compound represented by the above generalformula (1) can be synthesized by a known method from a maleimidecompound having a hydroxyl group and a compound reactive to the hydroxylgroup. Examples of the compound reactive to the hydroxyl group includedi-, tri-, penta-, and hexa-carboxylic acids having an average molecularweight of 100 to 1,000,000, having two to six carboxyl groups, etherbonds, or ester bonds in one molecule, and having one unit or repeatingunits in which at least one hydrocarbon group selected from the groupconsisting of a linear alkylene group, a branched alkylene group, acycloalkylene group, and an aryl group is bonded via an ether bondand/or an ester bond, (poly)isocyanates, carbonic acid esters, phosgene,and the like.

As the polymerization precursors, in addition to the above, thefollowing compounds may be mentioned.

Examples of the compounds having one maleimide group includemethylmaleimide, hexylmaleimide, N-phenylmaleimide,N-(2-tert-butylphenyl)maleimide, N-(2-fluorophenyl)maleimide,N-(2-chlorophenyl)maleimide, N-(2-bromophenyl)maleimide,N-(2-iodophenyl)maleimide, N-cyclohexylmaleimide, N-laurylmaleimide,N,N′-methylenebis(N-phenyl)monomaleimide, hydroxymethylmaleimide,hydroxyethylmaleimide, 2-ethyl carbonate-ethylmaleimide,2-isopropylurethane-ethylmaleimide, 2-acryloylethylmaleimide,acetoxyethylmaleimide, aminophenylmaleimide, N-(2-CF₃-phenyl)maleimide,N-(4-CF₃-phenyl)maleimide, N-(2-CF₃-phenyl)methylmaleimide,N-(2-bromo-3,5-CF₃-phenyl)maleimide, and the like.

Examples of the compounds having two or more maleimide groups includeN,N′-ethylenebismaleimide, N,N′-hexamethylenebismaleimide,N,N′-4,4′-biphenylbismaleimide, N,N′-3,3′-biphenylbismaleimide,N,N′-(4,4′-diphenylmethane)bismaleimide,N,N′-3,3-diphenylmethanebismaleimide,N,N′-4,4-diphenylmethanebismaleimide,N,N′-methylenebis(3-chloro-p-phenylene)bismaleimide,N,N′-4,4′-dicyclohexylmethanebismaleimide,N,N′-(2,2′-diethyl-6,6′-dimethyl-4,4′-methylenediphenylene)bismaleimide,N,N′-1,2-phenylenebismaleimide, N,N′-1,3-phenylenebismaleimide,N,N′-1,4-phenylenebismaleimide, 2,2′-bis(4-N-maleimidephenyl)propane,2,2′-bis[4-(4-N-maleimidephenoxy)phenyl]propane,2,2′-bis[3-tert-butyl-5-methyl-4-(4-maleimidephenoxy)phenyl]propane,2,2′-bis(4-N-maleimide-2-methyl-5-ethylphenyl)propane,2,2′-bis(4-N-maleimide-2,5-dibromophenyl)propane,bis(4-N-maleimidephenyl)methane,bis(3,5-dimethyl-4-maleimidephenyl)methane,bis(3-ethyl-5-methyl-4-maleimidephenyl)methane,bis(3,5-diethyl-4-maleimidephenyl)methane,bis(3-methyl-4-maleimidephenyl)methane,bis(3-ethyl-4-maleimidephenyl)methane, m-di-N-maleimidebenzene,2,6-bis[2-(4-maleimidephenyl)propyl]benzene,N,N′-2,4-toluylenebismaleimide, N,N′-2,6-toluylenebismaleimide,N,N′-4,4-diphenyl ether bismaleimide, N,N′-3,3-diphenyl etherbismaleimide, N,N′-4,4-diphenyl sulfide bismaleimide, N,N′-3,3-diphenylsulfide bismaleimide, N,N′-4,4-diphenyl sulfone bismaleimide,N,N′-3,3-diphenyl sulfone bismaleimide, N,N′-4,4-diphenyl sulfonebismaleimide, N,N′-4,4-diphenyl ketone bismaleimide, N,N′-3,3-diphenylketone bismaleimide, N,N′-4,4-diphenyl-1,1-propanebismaleimide,N,N′-3,3-diphenyl-1,1-propanebismaleimide,3,3′-dimethyl-N,N′-4,4-diphenylmethanebismaleimide,3,3′-dimethyl-N,N′-4,4′-biphenylbismaleimide,1,3-bis(3-maleimidephenoxybenzene, bis(4-maleimidephenyl)methane,bis[4-(3-maleimidephenoxy)phenyl]methane,2,2-bis[4-(4-maleimidephenoxy)phenyl]methane,1,1-bis[4-(4-maleimidephenoxy)phenyl]methane,1,1-bis[3-methyl-4-(4-maleimidephenoxy)phenyl]methane,1,1-bis[3-chloro-4-(4-maleimidephenoxy)phenyl]methane,1,1-bis[3-bromo-4-(4-maleimidephenoxy)phenyl]methane,1,1-bis[4-(3-maleimidephenoxy)phenyl]ethane,1,2-bis[4-(3-maleimidephenoxy)phenyl]ethane,1,1-bis[4-(4-maleimidephenoxy)phenyl]ethane,1,1-bis[3-methyl-4-(4-maleimidephenoxy)phenyl]ethane,1,1-bis[3-chloro-4-(4-maleimidephenoxy)phenyl]ethane,1,1-bis[3-bromo-4-(4-maleimidephenoxy)phenyl]ethane,2,2-bis(4-maleimidephenyl)propane,2,2-bis[4-(3-maleimidephenoxy)phenyl]propane,2,2-bis[4-(4-maleimidephenoxy)phenyl]propane,2,2-bis[3-chloro-4-(4-maleimidephenoxy)phenyl]propane,2,2-bis[3-bromo-4-(4-maleimidephenoxy)phenyl]propane,2,2-bis[3-ethyl-4-(4-maleimidephenoxy)phenyl]propane,2,2-bis[3-propyl-4-(4-maleimidephenoxy)phenyl]propane,2,2-bis[3-isopropyl-4-(4-maleimidephenoxy)phenyl]propane,2,2-bis[3-butyl-4-(4-maleimidephenoxy)phenyl]propane,2,2-bis[3-sec-butyl-4-(4-maleimidephenoxy)phenyl]propane,2,2-bis[3-methoxy-4-(4-maleimidephenoxy)phenyl]propane,1,1-bis[4-(4-maleimidephenoxy)phenyl]propane,2,2-bis[4-(3-maleimidephenoxy)phenyl]butane,3,3-bis[4-(4-maleimidephenoxy)phenyl]pentane,4,4′-bis(3-maleimidephenoxy)biphenyl,bis[4-(3-maleimidephenoxy)phenyl]ketone,bis[4-(3-maleimidephenoxy)phenyl]sulfoxide,bis[4-(3-maleimidephenoxy)phenyl]sulfone,bis[4-(3-maleimidephenoxy)phenyl]ether, N,N′-p-benzophenonebismaleimide, N,N′-dodecamethylenebismaleimide,N,N′-m-xylylenebismaleimide, N,N′-p-xylylenebismaleimide,N,N′-1,3-bismethylenecyclohexanebismaleimide,N,N′-1,4-bismethylenecyclohexanebismaleimide,N,N′-2,4-tolylenebismaleimide, N,N′-2,6-tolylenebismaleimide,N,N′-diphenylethanebismaleimide, N,N′-diphenyl ether bismaleimide,N,N′-(methylene-ditetrahydrophenyl)bismaleimide,N,N′-(3-ethyl)-4,4-diphenylmethanebismaleimide,N,N′-(3,3-dimethyl)-4,4-diphenylmethanebismaleimide,N,N′-(3,3-diethyl)-4,4-diphenylmethanebismaleimide,N,N′-(3,3-dichloro)-4,4-diphenylmethanebismaleimide,N,N′-tolidinebismaleimide, N,N′-isophoronebismaleimide,N,N′-p,p′diphenyldimethylsilylbismaleimide,N,N′-benzophenonebismaleimide, N,N′-diphenylpropanebismaleimide,N,N′-naphthalenebismaleimide,N,N′-4,4-(1,1-diphenyl-cyclohexane)bismaleimide,N,N′-3,5-(1,2,4-triazole)bismaleimide,N,N′-pyridine-2,6-diylbismaleimide,N,N′-5-methoxy-1,3-phenylenebismaleimide,1,2-bis(2-maleimideethoxy)ethane, 1,3-bis(3-maleimidepropoxy)propane,N,N′-4,4-diphenylmethane-bis-dimethylmaleimide,N,N′-hexamethylene-bis-dimethylmaleimide, N,N′-4,4′-(diphenylether)-bis-dimethylmaleimide, N,N′-4,4′-(diphenylsulfone)-bis-dimethylmaleimide, triethylene glycol biscarbonatebisethylmaleimide, isophorone bisurethane bisethylmaleimide,bisethylmaleimide carbonate, 4,9-dioxa-1,12dodecanebismaleimide,bispropylmaleimide, dodecaneN,N′-bismaleimide,N-(2,4,6-isopropyl-3-maleimidephenyl)maleimide, and the like.

In addition, maleimide-based compounds obtainable by the reaction of3,4,4′-triaminodiphenylmethane, triaminophenol, and the like with maleicanhydride and maleimide-based compounds obtainable by the reaction oftris-(4-aminophenyl)-phosphate or tris-(4-aminophenyl)-thiophosphatewith maleic anhydride may be also mentioned.

Moreover, examples of the fluorine-containing bismaleimide-basedcompounds include 2,2′-bis(4-maleimidephenyl)hexafluoropropane,2,2′-bis[4-(3-maleimidephenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2′-bis[4-(4-maleimidephenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2′-bis[4-(4-maleimide-2-trifluoromethylphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2-bis[3,5-dimethyl-(4-maleimidephenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2-bis[3,5-dibromo-(4-maleimidephenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2-bis[3,5-dimethyl-(4-maleimidephenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2′-bis[3-maleimide-5-(trifluoromethyl)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2′-bis(3-fluoro-5-maleimidephenyl)-1,1,1,3,3,3-hexafluoropropane,3,3′-bismaleimide-5,5′-bis(trifluoromethyl)biphenyl,3,3′-difluoro-5,5′-bismaleimidebiphenyl,3,3′-bismaleimide-5,5′-bis(trifluoromethyl)benzophenone,3,3′-difluoro-5,5′-bismaleimidebenzophenone,1,3-bis[3-maleimide-5-(trifluoromethyl)phenoxy]benzene,1,4-bis[3-maleimide-5-(trifluoromethyl)phenoxy]benzene,1,3-bis(3-fluoro-5-maleimidephenoxy)benzene,1,4-bis(3-fluoro-5-maleimidephenoxy)benzene,1,3-bis(3-fluorophenoxy)-5-fluorobenzene,1,3-bis(3-fluoro-5-maleimidephenoxy)-5-fluorobenzene,3,5-bis[3-maleimidephenoxy]benzotrifluoride,3,5-bis[3-maleimide-5-(trifluoromethyl)phenoxy]benzotrifluoride,bis(3-fluoro-5-maleimidephenyl) ether,bis[3-maleimide-5-(trifluoromethyl)phenyl]ether,bis(3-fluoro-5-maleimidephenyl) sulfide,bis[3-maleimide-5-(trifluoromethyl)phenyl]sulfide,bis(3-fluoro-5-maleimidephenyl) sulfone,bis[3-maleimide-5-(trifluoromethyl)phenyl]sulfone,1,3-bis(3-fluoro-5-maleimidephenyl)-1,1,3,3-tetramethyldisiloxane,1,3-bis[3-maleimide-5-(trifluoromethyl)phenyl]-1,1,3,3-tetramethyldisiloxane,and the like.

In addition, as the maleimide-based compounds, oligomers and polymershaving one or more maleimide groups are also mentioned.

The kind of the oligomers is not particularly limited and examples ofthe oligomers include those obtainable by Michael addition reaction ofthe above maleimide-based compounds with polyamines, those obtainable bythe reaction of maleic acids and/or maleic anhydrides with diamines, andthe like. Moreover, those obtainable by the reaction of polyimideprecursors having a terminal anhydride group, obtained by reactingtetracarboxylic dianhydrides and diamines, with hydroxylgroup-containing maleimide-based compounds such as maleimide-basedcompounds of the reaction products between epoxy resins and maleimidegroup-containing monocarboxylic acids, those obtainable by the reactionof polyimide precursors having a terminal anhydride group, obtained byreacting tetracarboxylic dianhydrides and diamines, with hydroxylgroup-containing maleimide-based compounds such as maleimide-basedcompounds of the reaction products between epoxy resins and maleimidegroup-containing monocarboxylic acids, and also with polyol compounds,and the like may be mentioned.

Furthermore, there may be mentioned compounds obtainable by bonding oneor more maleimide groups to polymer components or oligomer componentssuch as urethane resins, epoxy resins, polyester resins, polyetherresins, alkyd resins, polyvinyl chloride resins, fluorocarbon resins,silicone resins, vinyl acetate resins, phenol resins, polyamide resins,and modified resins of two or more of them.

Examples of the compound having one or more (meth)acryloyl groupsinclude (meth)acryl esters such as methyl (meth)acrylate, ethyl(meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl(meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl(meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, lauryl(meth)acrylate, lauryl-tridecyl (meth)acrylate, tridecyl (meth)acrylate,cetyl-stearyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl(meth)acrylate, benzyl (meth)acrylate, and phenyl (meth)acrylate;(meth)acrylamides such as (meth)acrylamide and methylol(meth)acrylamide; reactive acrylic monomers such as (meth)acrylic acid,hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl(meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl(meth)acrylate, butylaminoethyl (meth)acrylate, glycidyl (meth)acrylate,and tetrahydrofurfuryl (meth)acrylate; crosslinkable acrylic monomerssuch as ethylene di(meth)acrylate, diethylene glycol di(meth)acrylate,triethylene glycol di(meth)acrylate, tetraethylene glycoldi(meth)acrylate, decaethylene glycol di(meth)acrylate,pentadecaethylene glycol di(meth)acrylate, pentacontahectaethyleneglycol di(meth)acrylate, butylene di(meth)acrylate, allyl(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, and diethylene glycol phthalate di(meth)acrylate;monofunctional (meth)acrylic compounds such as diethyleneglycol-modified nonylphenol (meth)acrylate, isodecyl (meth)acrylate,lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and2-(2-ethoxyethoxy)2-ethylhexyl (meth)acrylate; and the like.

In addition to the above, examples of the compound having two or more(meth)acryloyl groups include 1,4-butanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, propylene oxide-modified neopentyl glycoldi(meth)acrylate, neopentyl glycol hydroxypropionate di(meth)acrylate,neopentyl glycol hydroxypivalate di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tripropylene glycoldi(meth)acrylate, polypropylene glycol di(meth)acrylate,trimethylolpropane tri(meth)acrylate, ethylene oxide-modifiedtrimethylolpropane tri(meth)acrylate, propylene oxide-modifiedtrimethylolpropane tri(meth)acrylate, propylene oxide-modified glycerintri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate,dipentaerythritol hexa(meth)acrylate, and isocyanuric acid ethyleneoxide-modified tri(meth)acrylate; and the like.

In addition, there are mentioned isobornyl (meth)acrylate, norbornyl(meth)acrylate, dicyclopentenoxyethyl (meth)acrylate,dicyclopentenoxypropyl (meth)acrylate, etc.; (meth)acryl ester ofdiethylene glycol dicyclopentenyl monoether, (meth)acryl ester ofoligooxyethylene or oligopropylene glycol dicyclopentenyl monoether,etc.; dicyclopentenyl cinnamate, dicyclopentenoxyethyl cinnamate,dicyclopentenoxyethyl monofumarate or difumarate, etc.; mono- ordi-(meth)acrylates of3,9-bis(1,1-bismethyl-2-oxyethyl)-spiro[5,5]undecane,3,9-bis(1,1-bismethyl-2-oxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane,3,9-bis(2-oxyethyl)-spiro[5,5]undecane,3,9-bis(2-oxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, etc., or mono-or di-(meth)acrylates of ethylene oxide or propylene oxide additionpolymers of these spiro glycols, or methyl ethers of thesemono(meth)acrylates, 1-azabicyclo[2,2,2]-3-octenyl (meth)acrylate,bicyclo[2,2,1]-5-hepten-2,3-dicarboxyl monoallyl ester, etc.,dicyclopentadienyl (meth)acrylate, dicyclopentadienyloxyethyl(meth)acrylate, dihydroxydicyclopentadienyl (meth)acrylate, and thelike.

In addition, oligomers and polymers having one or more (meth)acryloylgroups are also mentioned.

The kind of the oligomers is not particularly limited and examples ofthe oligomers include oligoethylene glycols, epoxy resin oligomers,polyester resin oligomers, polyamide resin oligomers, urethane resinoligomers, oligovinyl alcohol, phenol resin oligomers, and the like.

Specific examples thereof include acryl esters of epoxy resin oligomers(e.g., diglycidyl ether diacrylate of bisphenol A), reaction productsamong epoxy resin oligomers, acrylic acid, and methyltetrahydrophthalicanhydride, reaction products between epoxy resin oligomers and2-hydroxyethyl acrylate, reaction products among epoxy resin oligomers,diglycidyl ether, and diallylamine, ring-opening copolymerization estersof glycidyl diacrylate and phthalic anhydride, esters of methacrylicacid dimer and polyols, polyesters obtainable from acrylic acid,phthalic anhydride, and propylene oxide, reaction products amongoligoethylene glycols, maleic anhydride, and glycidyl methacrylate,reaction products between oligovinyl alcohols and N-methylolacrylamide,compounds obtainable by esterifying oligovinyl alcohols with succinicanhydride and then adding glycidyl methacrylate, oligomers obtainable byreacting diallyl ester of pyromellitic dianhydride withp,p′-diaminodiphenyl, reaction products between ethylene-maleicanhydride copolymers and allylamine, reaction products between methylvinyl ether-maleic anhydride copolymers and 2-hydroxyethyl acrylate,compounds obtainable by further reacting the products with glycidylmethacrylate, urethane oligomers which have acryloyl groups ormethacryloyl groups in both terminals and in which an oligooxyalkylenesegment or a saturated oligoester segment or both of them are connectedvia a urethane bond, acryl-modified isoprene rubber or butadiene rubberat the terminals, and the like.

Moreover, specific examples of the oligomers having a (meth)acryloylgroup include oligoethylene glycol di(meth)acrylate, nonylphenolEO-modified (meth)acrylate, oligopropylene glycol di(meth)acrylate,neopentyl glycol di(meth)acrylate, butylene glycol di(meth)acrylate,1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate,pentaerythritol poly(meth)acrylate, bisphenol A diglycidyl etherdi(meth)acrylate, oligoester (meth)acrylate, oligoester (meth)acrylate,and the like.

Moreover, there are also mentioned (meth)acryloyl group-containingsilicone oligomers wherein one or more (meth)acryloyl groups or groupscontaining a (meth)acryloyl group are bonded to at least one terminalsilicon. Examples of the structure of the silicone oligomer itselfinclude structures containing any one or more of an alkylsiloxanestructural unit having 2 or more carbon atoms, an arylsiloxanestructural unit, and an aralkylsiloxane structural unit.

Furthermore, there are also mentioned compounds obtainable by bondingone or more (meth)acryloyl groups to polymer components or oligomercomponents such as urethane resins, epoxy resins, polyester resins,polyether resins, alkyd resins, polyvinyl chloride resins, fluorocarbonresins, silicone resins, vinyl acetate resins, phenol resins, polyamideresins, and modified resins of two or more of them.

As compounds having one or more cyclic ether structures, cyclic ethercompounds having a cyclic ether structure containing 2 to 12 carbonatoms and 1 to 6 oxygen atoms, particularly one or more crosslinkagestructures containing —O— are mentioned. More specifically, compoundshaving an epoxy ring such as a glycidyl group are mentioned.

Examples of the compound having one or more cyclic ether structuresinclude ethylene glycol diglycidyl ether, trimethylolpropane triglycidylether, and the like.

Moreover, oligomers and polymers having one or more cyclic etherstructures are also mentioned.

Examples of the oligomers having a cyclic ether structure includeoligoethylene glycol diglycidyl ether and the like.

Furthermore, there are also mentioned compounds obtainable by bondingone or more groups having the cyclic ether structure to polymercomponents or oligomer components such as urethane resins, epoxy resins,polyester resins, polyether resins, alkyd resins, polyvinyl chlorideresins, fluorocarbon resins, silicone resins, vinyl acetate resins,phenol resins, polyamide resins, and modified resins of two or more ofthem.

As the compound having one or more alkenyl groups, compounds having oneor more vinyl groups and/or allyl groups are mentioned. As the compoundhaving one or more alkenyl groups, for example, polyvinyl cinnamates andthe like are mentioned.

Furthermore, there are also mentioned compounds obtainable by bondingone or more alkenyl groups to polymer components or oligomer componentssuch as urethane resins, epoxy resins, polyester resins, polyetherresins, alkyd resins, polyvinyl chloride resins, fluorocarbon resins,silicone resins, vinyl acetate resins, phenol resins, polyamide resins,and modified resins of two or more of them.

Examples of the compound having one or more vinylene groups includecompounds having an ethylenically unsaturated double bond, unsaturatedpolyesters, and the like. Moreover, as the compound having one or morevinylene groups, compounds having one or more cinnamyl groups(C₆H₅—CH═CH—CH₂—) or cinnamylidene groups (C₆H₅—CH═CH—CH═) are alsomentioned. As such compounds, for example, polyvinyl cinnamate ismentioned. Polyvinyl cinnamate can be obtained by reacting polyvinylalcohol with C₆H₅—CH═CH—CH₂—COCl.

Furthermore, there are also mentioned compounds obtainable by bondingone or more vinylene groups to polymer components or oligomer componentssuch as urethane resins, epoxy resins, polyester resins, polyetherresins, alkyd resins, polyvinyl chloride resins, fluorocarbon resins,silicone resins, vinyl acetate resins, phenol resins, polyamide resins,and modified resins of two or more of them.

Examples of the compound having one or more styryl groups includestyrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene,p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, chlorostyrene,bromostyrene, and the like. Also, polyvinylbenzalacetophenones,polyvinylstyrylpyridines, and the like are mentioned.

Furthermore, there are also mentioned compounds obtainable by bondingone or more styryl groups to polymer components or oligomer componentssuch as urethane resins, epoxy resins, polyester resins, polyetherresins, alkyd resins, polyvinyl chloride resins, fluorocarbon resins,silicone resins, vinyl acetate resins, phenol resins, polyamide resins,and modified resins of two or more of them.

Examples of the compound having one or more azido groups include2,6-bis(4-azidobenzylidene)cyclohexanone,2,6-bis(4′-azidobenzyl)methylcyclohexanone, and the like.

Furthermore, there are also mentioned compounds obtainable by bondingone or more azido groups to polymer components or oligomer componentssuch as urethane resins, epoxy resins, polyester resins, polyetherresins, alkyd resins, polyvinyl chloride resins, fluorocarbon resins,silicone resins, vinyl acetate resins, phenol resins, polyamide resins,and modified resins of two or more of them.

Moreover, as a monomer copolymerizable with the above monomers, cyanogroup-containing vinyl compounds such as acrylonitrile andmethacrylonitrile; halogen-containing vinyl compounds such as vinylchloride and vinylidene chloride; organic acid group-containing vinylcompounds such as vinyl acetate and vinyl propionate; reactive monomerssuch as ethylene, maleic acid and itaconic acid; acryl-modifiedsilicones; crosslinking copolymerization monomers such as chloroethylvinyl ether, allyl glycidyl ether, ethylidenenorbornene, divinylbenzene,triallyl cyanurate, and triallyl isocyanurate; and the like.

The above polymerization precursor may be used singly or as a mixture oftwo or more of them.

Furthermore, it is also possible to change the composition of theresulting polymer, for example, in the direction of the film thicknessor in the direction perpendicular to the surface of the base material bychanging the composition of the polymerization precursor to bepolymerized during the polymerization, and the like.

In the case of polymerizing a polymerization precursor other thanspontaneously photopolymerizable compounds, a photopolymerizationinitiator is necessary. The photopolymerization initiator is notparticularly limited as far as it dissolves in the supercritical fluidor subcritical fluid or the polymerization precursor, and can besuitably determined depending on the supercritical fluid or subcriticalfluid and the polymerization precursor to be used, and the like.

Examples of the photopolymerization initiator include azo initiatorssuch as dialkyl (2,2′-azobisisobutyrate), e.g., dimethyl(2,2′-azobisisobutyrate) and diethyl (2,2′-azobisisobutyrate),2,2′-azobis(isobutyronitrile)(AIBN), 2,2′-azobis(2-methylbutyronitrile),and 2,2′-azobis(2,4-dimethylvaleronitrile); peroxide initiators such astert-butyl hydroperoxide, cumene hydroperoxide, tert-butylperoxyneodecanoate, tert-butyl peroxypivalate, tert-hexylperoxy-2-ethylhexanoate, methyl ethyl ketone peroxide, acetylcyclohexylsulfonyl peroxide, lauroyl peroxide, and benzoyl peroxide; andthe like.

Examples of the other photopolymerization initiator include benzoin,benzoin alkyl ethers such as benzoin ethyl ether, benzoin-n-propyl etherand benzoin isbutyl ether; 2,2-dimethoxy-2-phenylacetophenone,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one,1-hydroxycyclohexyl phenyl ketone, diacetyl, diphenyl sulfide, eosin,thionine, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, and the like.

As the photopolymerization initiator, there are further mentionedaromatic carbonyl compounds such as benzophenone, benzoin methyl ether,benzoin isopropyl ether, benzil, xanthone, thioxanthone, andanthraquinone; acetophenones such as acetophenone, propiophenone,α-hydroxyisobutyrophenone, α,α′-dichloro-4-phenoxyacetophenone,1-hydroxy-1-cyclohexylacetophenone, and acetophenone; organic peroxidessuch as benzoyl peroxide, tert-butyl-peroxybenzoate,tert-butyl-peroxy-2-ethylhexanoate, tert-butyl hydroperoxide,di-tert-butyl diperoxyisophthalate, and3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone; diphenyl haloniumsalts such as diphenyliodonium bromide and diphenyliodonium chloride;organic halides such as carbon tetrachloride, carbon tetrabromide,chloroform, and iodoform; heterocyclic and polycyclic compounds such as3-phenyl-5-isoxazolone and2,4,6-tris(trichloromethyl)-1,3,5-triazinebenzanthrone; azo compoundssuch as 2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobisisobutyronitrile, 1,1′-azobis(cyclohexane-1-carbonitrile),and 2,2′-azobis(2-methylbutyronitrile); iron-arene complexes describedin European Patent No. 152377; titanocene compounds described inJapanese Patent Application Laid-open No. 63-221110; and the like.

The above photopolymerization initiator may be used singly or as amixture of two or more of them.

The using amount of the photopolymerization initiator can be suitablydetermined and can be, for example, about 0.1 to 30 parts by weightrelative to 100 parts by weight of the polymerization precursor.

Also, if necessary, the above photopolymerization initiator can be usedin combination with a photopolymerization initiating auxiliary(sensitizer). Examples of the photopolymerization initiating auxiliaryinclude 2-dimethylaminoethyl benzoate, N,N′-dimethylaminoethylmethacrylate, isoamyl p-dimethylaminobenzoate, and ethylp-dimethylaminobenzoate; and the like.

In the invention, a spectral sensitizer which may interact with thepolymer to be produced or the photopolymerization initiator can be used.Examples of the spectral sensitizer include thioxanthene-based,xanthene-based, ketone-based, thiopyrylium salt-based, basestyryl-based, merocyanine-based, 3-substituted coumarin-based,cyanine-based, acridine-based, thiazine-based, and the like pigments. Inthis connection, the “interaction” herein includes energy transfer andelectron transfer from an excited spectral sensitizer to the polymer tobe produced and/or the photopolymerization initiator.

The following will describe one embodiment of the method of producing apolymer of the invention with reference to the Drawing. FIG. 1illustrates a schematic constitutional drawing of one example ofproduction apparatus. 1 is a carbon dioxide cylinder, 2 is a pump forcarbon dioxide supply, 3 is a reactor capable of maintaining a hightemperature and high pressure state, 4 is a temperature-controllingmeans, 5 is a window for the incidence of an activation energy ray(e.g., quartz window), 5′ is a window (e.g., quartz window), 6 is alight source, 7 is a pressure-reducing valve, 8 is a base materialthrough which an activation energy ray can be transmitted (activationenergy ray-transmittable base material), 9 is a magnetic stirrer, and 10is a stirring bar (rotor). In this connection, the window 5′ is notnecessarily provided.

First, the activation energy ray-transmittable base material 8 is placedinside the activation energy ray-transmittable window 5 set up at thereactor 3. The activation energy ray-transmittable base material 8 isplaced so that the surface at the side of the window 5 which is asurface thereof through which the activation energy ray is incident isnot exposed to the supercritical carbon dioxide or subcritical carbondioxide and another surface thereof through which the activation energyray is outgoing is exposed to the supercritical carbon dioxide orsubcritical carbon dioxide at the polymerization reaction. Theactivation energy ray-transmittable base material 8 is not necessarilyplaced so as to be contact with the window 5 and a placing member suchas an activation energy ray-transmittable film can intervenes betweenthem.

The method for fixing the activation energy ray-transmittable basematerial 8 is not particularly limited, and examples thereof include amethod of providing the window at the bottom of a concave portion of thereactor wall and pushing the base material thereinto to adhere itclosely to the window, a method of fitting the base material to thewindow frame with a fastener, and the like method. Alternatively, it isalso possible that the window is constituted as a removable one and thewindow itself is used as a base material.

The base material is not particularly limited as far as it transmits anactivation energy ray, and examples thereof include transparent resinsor translucent resins, transparent or translucent glass, metal oxidessuch as ITO (indium-tin oxide), metals, and the like. The material ofthe base material is selected in consideration of the composition of thepolymer film to be formed and the like. For example, in the case offorming a bismaleimide-based polymer film, when the base material isquartz glass, the adhesiveness of the polymer film to be formed is lowand hence it is easy to peel it off. On the other hand, when the basematerial is a PET (polyethylene terephthalate) film, a polymer filmhaving a high adhesiveness is formed. In addition, a base materialcoated with a coating material such as polyvinyl alcohol (PVA) can beused.

As the base material, the material having any shape can be used. Thepolymerization precursor dissolved in the supercritical fluid orsubcritical fluid polymerizes in a state of being homogeneouslydistributed on the interface of the base material to form a polymerfilm. Therefore, it is possible to form a polymer film uniformly even onthe base material having a fine concavo-convex structure or a deepconcavo-convex structure.

Moreover, with regard to the window 5 for the incidence of theactivation energy ray on which the base material 8 is placed or theplacing member to be set up thereon, the shape of them can be determinedaccording to the shape of the base material for forming the polymer filmor the desired shape of the polymer film.

After the activation energy ray-transmittable base material 8 is placedinside the reactor 3, a polymerization precursor and, if necessary, aphotopolymerization initiator are charged into the reactor 3. In thecase that the polymerization precursor is liquid, the polymerizationprecursor and, if necessary, the photopolymerization initiator can besupplied from their reservoir(s) to the reactor 3 by a pump. Thepolymerization precursor and the photopolymerization initiator can besupplied to the reactor 3 after adjusting their temperature topolymerization temperature beforehand by a heater.

On the other hand, carbon dioxide is supplied from the carbon dioxidecylinder 1 to the reactor 3 by the pump 2. Carbon dioxide can besupplied to the reactor 3 after regulating its temperature topolymerization temperature beforehand by a heater.

The pressure in the reactor 3 is regulated to polymerization pressure bythe amount of carbon dioxide supplied. On the other hand, thetemperature in the reactor 3 is regulated to polymerization temperatureby the temperature-controlling means 4 such as a heater. The regulationof the pressure in the reactor 3 and the regulation of the temperaturein the reactor 3 can be carried out simultaneously, or either of themmay be first regulated and then the other may be regulated.

In the case that the polymerization precursor and carbon dioxide whosetemperature is regulated to polymerization temperature or highertemperature beforehand by a heater are supplied to the reactor 3, thetemperature-controlling means 4 such as a heater is not necessarilyprovided as far as the temperature in the reactor 3 can be maintained topolymerization temperature during the polymerization reaction.

After the inside of the reactor 3 are maintained at predeterminedpressure and temperature, a photopolymerization reaction is carried outby irradiating the inside of the reactor 3 with an activation energy raythrough the activation energy ray transmittable window 5 and the basematerial 8 from the light source 6 with stirring the inside of thereactor by the magnetic stirrer 9 and the stirring bar 10, whereby apolymer film is formed on the activation energy ray outgoing surface ofthe activation energy ray-transmittable base material. The activationenergy ray may be applied as continuous irradiation or as intermittentirradiation. By controlling the dose of the activation energy ray, it ispossible to control the thickness of the polymer film to be formed.

In this connection, the stirring means for stirring the inside of thereactor is not limited to the magnetic stirrer 9 and the stirring bar10.

Moreover, according to the invention, the polymer film can beselectively formed on the activation energy ray-transmitted part of theactivation energy ray outgoing surface of the base material. Forexample, by irradiation with an activation energy ray through a maskpattern, a polymer film having a desired pattern can be formed. In thiscase, for example, it is possible to put a mask pattern on the outsideof the window 5 or to make the shape of the window itself apredetermined pattern shape.

Furthermore, by using a laser beam as a light source, a polymer filmhaving a fine pattern can be formed since the light-irradiated area canbe further focused as compared with the other light sources. Also, byusing a laser beam as a light source, irradiation with more highlyintense light can be achieved as compared with the other light sourcesand hence the density and the aspect (ratio of the height to thediameter of the furry protrusion) of the furry protrusion of the polymercontaining the furry protrusion can be more easily controlled.

After the completion of the polymerization reaction, carbon dioxide isreleased by the pressure-reducing valve 7 and the pressure in thereactor 3 is reduced to around atmospheric pressure. In order to removethe unreacted polymerization precursor and the like and to obtain morehighly pure polymer, the pressure in the reactor 3 may be reduced to apressure lower than atmospheric pressure, for example, a vacuum of 133Pa or lower and then be raised to around atmospheric pressure. Aftercooling the temperature in the reactor 3 to about room temperature, thebase material 8 on which a polymer film has been formed is taken out ofthe reactor 3.

After the completion of the polymerization reaction, the polymerproduced can be expanded by rapidly reducing the pressure from a highpressure state, i.e., a supercritical sate or a subcritical state or byrapidly cooling the temperature and rapidly reducing the pressure from ahigh temperature and high pressure state. A supercritical fluid orsubcritical fluid has a strong permeability into a polymer and ishomogeneous, a uniform porous substance can be formed by carrying outsuch a treatment.

At that time, the cooling rate of the polymer and the pressure-reducingrate of the polymer can be suitably determined. It is possible tocontrol the pore size by controlling the cooling rate of the polymer andthe pressure-reducing rate of the polymer. There is a tendency thatfaster cooling rate of the polymer and faster pressure-reducing rate ofthe polymer result in larger pore size.

In this connection, after the polymerization, according to need, thepolymer may be left in the supercritical fluid or subcritical fluid fora predetermined time and then rapid reduction of the pressure or rapidcooling and rapid reduction of the pressure may be carried out to expandthe polymer.

The polymer film formed on the base material which has been taken out ofthe reactor 3 can be post-cured by irradiation with an electromagneticwave, irradiation with a light or heating, or by the combinationthereof.

Carbon dioxide released from the inside of the reactor 3 after thecompletion of the polymerization reaction can be recovered and re-used.

Although the above polymerization steps are described as batch-wise, thepolymerization can be also carried out continuously orsemi-continuously.

The shape of the reactor for use in carrying out the method of producinga polymer of the invention is not limited to the one illustrated inFIG. 1. For example, a constitution wherein an optical system such as anoptical fiber is inserted into the reactor is possible, where anactivation energy ray can be applied to the inside of the reactorthrough the optical system.

Furthermore, by suitably selecting the polymerization conditions of thedose of the activation energy ray and the like, a polymer containing afurry protrusion can be also formed on the base material. In this case,the polymer grows along the direction of irradiation with the activationenergy ray, whereby the furry protrusion of the polymer is formed. Thatis, the polymer usually grows in the direction perpendicular to the basematerial surface, whereby the furry protrusion of the polymer is formed.Usually, there is a tendency that the polymer to be produced changesfrom the polymer containing the furry protrusion into a continuous film,when the irradiation time with the activation energy ray (polymerizationtime) is lengthened.

According to the invention, there can be produced a polymer having afurry protrusion whose height is 0.1 time or more as much as thediameter, or a polymer having a furry protrusion whose height is 1 timeor more as much as the diameter, or a polymer having a furry protrusionwhose height is 2 times or more as much as the diameter, or a polymerhaving a furry protrusion whose height is 3 times or more as much as thediameter, or further a polymer having a furry protrusion whose height is5 times or more as much as the diameter. The upper limit of the ratio ofthe height to the diameter of the furry protrusion is not particularlylimited but, for example, the height of the furry protrusion can be 50times as much as the diameter.

Moreover, according to the invention, there can be produced a polymerhaving a furry protrusion whose height is 10 nm or more, or a polymerhaving a furry protrusion whose height is 0.5 μm or more, or a polymerhaving a furry protrusion whose height is 1 μm or more, or a polymerhaving a furry protrusion whose height is 5 μm or more, or a polymerhaving a furry protrusion whose height is 10 μm or more, or a polymerhaving a furry protrusion whose height is 30 μm or more, or further apolymer having a furry protrusion whose height is 50 μm or more. Theupper limit of the height of the furry protrusion is not particularlylimited but, for example, the height of the furry protrusion can be 500μm.

The height of the furry protrusion of the polymer can be controlled bythe dose of the activation energy ray (integrating amount of light). Theheight of the furry protrusion of the polymer is nearly proportional tothe dose of the activation energy ray, but there is a tendency that theheight of the furry protrusion of the polymer no longer increases andthe distance between the furry protrusions is narrowed to form acontinuous film when the dose of the activation energy ray reaches acertain amount or more.

In particular, according to the invention, there can be produced apolymer having a furry protrusion whose height is 0.1 time or more asmuch as the diameter and is 10 nm or more, or a polymer having a furryprotrusion whose height is 1 time or more as much as the diameter and is1 μm or more, or further a polymer having a furry protrusion whoseheight is 5 times or more as much as the diameter and is 50 μm or more.The polymer having a furry protrusion whose height is large to thediameter and is high is hitherto not obtained by polymerizing apolymerization precursor such as a monomer.

The surface density of the furry protrusions of the polymer containingthe furry protrusion is not particularly limited but, according to theinvention, it is possible to form a polymer containing the furryprotrusions having a high furry protrusion surface density of, forexample, 0.01 piece/nm² or higher, further 0.1 piece/nm² or higher onthe base material. Moreover, it is also possible to reduce the densityof the furry protrusions of the polymer containing the furry protrusionand the furry protrusion surface density can be controlled to be, forexample, 0.001 piece/μm².

Herein, in the case that the polymer containing the furry protrusion isa protruding polymer, the surface density of the furry protrusions meansthe density of the protruding polymer on the surface of the basematerial.

According to the invention, the polymer film or the polymer containingthe furry protrusion can be formed on the base material at the same timeas the polymerization reaction is carried out. Moreover, as mentionedabove, depending on the base material selected, the polymer film or thepolymer containing the furry protrusion to be formed can be easilypeeled off from the base material, so that the product can be obtained,for example, as a resin film (including the one having one or more furryprotrusions).

In addition, according to the invention, it is possible to form thepolymer film or the polymer containing the furry protrusion uniformlyeven on the base material having a fine concavo-convex structure or adeep concavo-convex structure. For example, according to the invention,it is possible to coat the inside of a minute reactor having a diameterof several dozen μm, which is called a microreactor.

Moreover, it is also possible to form a polymer film or a polymercontaining a furry protrusion, in which nano particles or the otheradditive is homogeneously dispersed. For example, a colored film or afluorescent film can be formed.

Furthermore, according to the invention, the polymer film or the polymercontaining the furry protrusion can be selectively formed on anactivation energy ray-transmitted part of the activation energy rayoutgoing surface of a base material. Therefore, it is possible to form apolymer film having a desired fine pattern or a furryprotrusion-containing polymer having a desired fine pattern. Forexample, the invention can be applied to the formation of a resist filmfor use in patterning of ITO.

In addition, the polymer film formed by photopolymerization of themaleimide-based compound represented by the above general formula (1)can be used as a covering layer of an optical element, a protective filmof an optical recording media, and the like.

Furthermore, the maleimide-based polymer film can be used as aninsulating film for semiconductor devices and wiring boards, amoisture-resistant protective film, a flexible printed board, and thelike.

In the case that polymer fine particles are produced according to themethod of the invention, when the polymer adheres to the window for theincidence of the activation energy ray, which is set up at the reactor,to inhibit the formation of the particles, it is effective to carry outthe photopolymerization reaction with placing a fluorocarbon resin filminside the window.

The invention can be also applied to the process for forming athree-dimensional structure by photopolymerization utilizing two-photonabsorption using the femtosecond laser described in S. Kawata et al.,Nature, 412, 697 (2001), the process for forming a fiber structure byphotopolymerization utilizing one-photon absorption using thefemtosecond laser described in S. Shoji and S. Kawata, Appl. Phys.Lett., 75, 737 (1999), and the process for forming a three-dimensionalphotonic crystal structure by photopolymerization utilizing theinterference light described in S. Shoji and S. Kawata, Appl. Phys.Lett., 76, 2668 (2000). By carrying out the above processes in asupercritical fluid or in a subcritical fluid, the influence of liquidfluctuation and the influence of viscosity can be reduced to form morefine structures as compared with the case of carrying out the processesin a liquid monomer.

EXAMPLES

The following will describe the invention in more detail with referenceto Examples. However, the invention is not limited to these Examples.

Example 1

Into a 30 cm³-volume pressure-resistant reactor having a quartzpressure-resistant window at the bottom of a concave portion provided atthe inner wall of the reactor was charged 1.5 g of a polyetherbismaleimide acetate (MIA-200 manufactured by Dainippon Ink & Chemicals,Incorporated) as a polymerization precursor. Then, carbon dioxide wasintroduced into the reactor with a cylinder pressure (about 7 MPa) understirring of the inside of the reactor. Thereafter, the temperature wasraised to 35° C. and carbon dioxide was further introduced by means of apressure pump so that the pressure in the reactor reached 30 MPa,whereby a supercritical state was achieved. The charged concentration ofthe polyether bismaleimide acetate as a polymerization precursor was 2%by weight.

After one hour of stirring under a pressure of 30 MPa at a temperatureof 37° C., the inside of the reactor was irradiated with an ultravioletray through the quartz pressure-resistant window from the outside of thereactor so that the dose reached 5.7 J/cm², using an ultrahigh pressuremercury lamp fitted with a quartz fiber as a light source. At that time,the irradiation with the ultraviolet ray was carried out underconditions of an irradiation intensity of 38 mW/cm² and an irradiationtime of 151 seconds. The wavelength of the ultraviolet ray for theirradiation was in the range of 254 to 436 nm. As a result, a polymerfilm was formed on the quartz pressure-resistant window.

After the irradiation with the ultraviolet ray, carbon dioxide wasgradually released to the outside of the reactor over a period of 120minutes to reduce the pressure in the reactor to atmospheric pressure.It was possible to peel off the polymer film formed on the quartzpressure-resistant window easily.

Example 2

A PET film as a base material was pushed into the concave portionprovided at the inner wall of the reactor, and was closely adhered andfixed to the quartz pressure-resistant window. Then, photopolymerizationwas carried out in the same way as Example 1, whereby a polymer film wasformed on the PET film. The polymer film formed on the PET film adheredtightly to the PET film and it was impossible to peel it off easily.

Example 3

A mask pattern was put on the outside of the quartz pressure-resistantwindow and photopolymerization was carried out in the same way asExample 1 except that the inside of the reactor was irradiated with theultraviolet ray through the mask pattern, whereby a polymer film towhich the mask pattern was transferred was formed on the ultravioletray-transmitted part of the quartz pressure-resistant window.

Example 4

After photopolymerization was carried out in the same way as Example 1,carbon dioxide was rapidly released to the outside of the reactor over aperiod of 10 minutes to reduce the pressure in the reactor toatmospheric pressure. When observed by an optical microscope, theresulting polymer film was found to be porous.

Comparative Example 1

Photopolymerization was carried out in the same way as Example 1 exceptthat the polymerization temperature was 18° C. and the polymerizationpressure was 4 MPa, but no polymer film was formed on the quartzpressure-resistant window. In this case, carbon dioxide during theirradiation with the ultraviolet ray was in a liquid state.

Comparative Example 2

Photopolymerization was carried out in the same way as Example 1 exceptthat acetone was used as a polymerization solvent, but no polymer filmwas formed on the quartz pressure-resistant window.

Example 5

Photopolymerization was carried out in the same way as Example 1 exceptthat 4.095 g of methyl methacrylate was used as a polymerizationprecursor and 0.123 g of2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 0.123 gof 1-hydroxycyclohexyl phenyl ketone were used as photopolymerizationinitiators, whereby polymer fine particles were formed in the reactor.In this case, the charged concentration of the methyl methacrylate asthe polymerization precursor was 15% by weight.

Example 6

Into a 30 cm³-volume pressure-resistant reactor having a quartzpressure-resistant window at the bottom of a concave portion provided atthe inner wall of the reactor was charged 0.872 g of a polyetherbismaleimide acetate (MIA-200 manufactured by Dainippon Ink & Chemicals,Incorporated) as a polymerization precursor. Then, carbon dioxide wasintroduced into the reactor with a cylinder pressure (about 7 MPa) understirring of the inside of the reactor. Thereafter, the temperature wasraised to 35° C. and carbon dioxide was further introduced by means of apressure pump so that the pressure in the reactor reached 30 MPa,whereby a supercritical state was achieved. The charged concentration ofthe polyether bismaleimide acetate as a polymerization precursor was3.5% by weight.

After one hour of stirring under a pressure of 30 MPa at a temperatureof 35° C., the inside of the reactor was irradiated with an ultravioletray through the quartz pressure-resistant window from the outside of thereactor so that the dose reached 1 J/cm², using an ultrahigh pressuremercury lamp fitted with a quartz fiber as a light source. At that time,the irradiation with the ultraviolet ray was carried out underconditions of an irradiation intensity of 33 mW/cm² and an irradiationtime of 30.3 seconds. The wavelength of the ultraviolet ray for theirradiation was in the range of 254 to 436 nm. As a result, a polymercontaining a furry protrusion which grew in the direction of irradiationwith the ultraviolet ray, i.e., in the direction perpendicular to thesurface of the base material was formed on the quartz pressure-resistantwindow.

After the irradiation with the ultraviolet ray, carbon dioxide wasgradually released to the outside of the reactor over a period of 120minutes to reduce the pressure in the reactor to atmospheric pressure.

FIG. 2 illustrates a SEM photograph of the resulting polymer containingthe furry protrusion.

Example 7

Photopolymerization was carried out in the same way as Example 6 exceptthat the irradiation with the ultraviolet ray was carried out underconditions of an irradiation intensity of 33 mW/cm² and an irradiationtime of 152 seconds and the dose of the ultraviolet ray was 5 J/cm²,whereby a polymer containing a furry protrusion which grew in thedirection of irradiation with the ultraviolet ray, i.e., in thedirection perpendicular to the surface of the base material was formedon the quartz pressure-resistant window.

FIG. 3 illustrates a SEM photograph of the resulting polymer containingthe furry protrusion.

Example 8

Photopolymerization was carried out in the same way as Example 6 exceptthat the irradiation with the ultraviolet ray was carried out underconditions of an irradiation intensity of 33 mW/cm² and an irradiationtime of 303 seconds and the dose of the ultraviolet ray was 10 J/cm²,whereby a polymer containing a furry protrusion which grew in thedirection of irradiation with the ultraviolet ray, i.e., in thedirection perpendicular to the surface of the base material was formedon the quartz pressure-resistant window.

FIG. 4 illustrates a SEM photograph of the resulting polymer containingthe furry protrusion.

Example 9

Photopolymerization was carried out in the same way as Example 6 exceptthat the irradiation with the ultraviolet ray was carried out underconditions of an irradiation intensity of 33 mW/cm² and an irradiationtime of 1515 seconds and the dose of the ultraviolet ray was 50 J/cm²,whereby a polymer film was formed on the quartz pressure-resistantwindow.

FIG. 5 illustrates a SEM photograph of the resulting polymer film. Inaddition, FIG. 6 illustrates a pattern sectional view of the resultingpolymer film. 11 is a base material (quartz pressure-resistant window)and 12 is a polymer film. In the polymer film obtained in Example 9, theconversion into a porous continuous film had proceeded as compared withthe polymer containing the furry protrusion obtained in Example 8.

Example 10

A mask pattern was put on the outside of the quartz pressure-resistantwindow and photopolymerization was carried out in the same way asExample 8 except that the inside of the reactor was irradiated with theultraviolet ray through the mask pattern, whereby a polymer containing afurry protrusion to which the mask pattern was transferred was formed onthe ultraviolet ray-transmitted part of the quartz pressure-resistantwindow.

INDUSTRIAL APPLICABILITY

According to the present invention, a polymerization precursor isphotopolymerized in a supercritical fluid or in a subcritical fluid,whereby, for example, a polymer film or a polymer containing a furryprotrusion can be produced. Furthermore, by irradiation of a basematerial with an activation energy ray through a mask pattern andtransmitting the ray, the polymer film or the polymer containing thefurry protrusion can be selectively formed on the activation energyray-transmitted part of the activation energy ray outgoing surface ofthe base material.

1. A method of producing a polymer comprising a step ofphotopolymerizing one or more photopolymerizable polymerizationprecursors on an activation energy ray-transmittable base material byirradiation with an activation energy ray in a supercritical fluid or ina subcritical fluid, said activation energy ray-transmittable basematerial being exposed to the supercritical fluid or subcritical fluid.2. The method of producing a polymer according to claim 1, wherein thesupercritical fluid or subcritical fluid is supercritical carbon dioxideor subcritical carbon dioxide.
 3. The method of producing a polymeraccording to claim 1, wherein the supercritical fluid or subcriticalfluid is carbon dioxide and the photopolymerizable polymerizationprecursor is photopolymerized in the carbon dioxide under a pressure of5 MPa or higher at a temperature of 20° C. or higher.
 4. The method ofproducing a polymer according to claim 1, wherein the supercriticalfluid or subcritical fluid is carbon dioxide and the photopolymerizablepolymerization precursor is photopolymerized in the carbon dioxide undera pressure of 7 MPa or higher at a temperature of 30° C. or higher. 5.The method of producing a polymer according to claim 1, wherein thephotopolymerizing step is conducted in the absence of aphotopolymerization initiator.
 6. The method of producing a polymeraccording to claim 1, wherein the photopolymerizable polymerizationprecursor has at least one maleimide group at the terminal.
 7. Themethod of producing a polymer according to claim 1, wherein theactivation energy ray is an ultraviolet ray, a visible light ray, or anear-infrared ray.
 8. The method of producing a polymer according toclaim 1, wherein the polymer to be produced is a film.
 9. The method ofproducing a polymer according to claim 1, wherein the photopolymerizablepolymerization precursor is represented by formula (1):

wherein A represents a hydrocarbon group optionally having asubstituent, or a (poly)ether connecting chain or a (poly)ether residue,(poly)ester connecting chain or a (poly)ester residue, (poly)urethaneconnecting chain or a (poly)urethane residue, or a (poly)carbonateconnecting chain or (poly)carbonate residue having a molecular weight of40 to 100,000 to which a hydrocarbon group optionally having asubstituent is bonded via at least one bond selected from the groupconsisting of an ether bond, an ester bond, a urethane bond, and acarbonate bond; B represents an ether bond, an ester bond, a urethanebond, or a carbonate bond; R represents a hydrocarbon group optionallyhaving a substituent; and m represents an integer of 1 to 6; providedthat all of B or R are not necessarily the same and two or more kinds ofB or R may be present when m is an integer of 2 or larger.
 10. Themethod of producing a polymer according to claim 9, wherein in formula(1), R is an alkylene group having 1 to 5 carbon atoms, B is an esterbond represented by —COO— or —OCO—, A is a (poly)ether connecting chainor (poly)ether residue (A-1) having a molecular weight of 100 to 1,000which comprises repeating units containing a linear alkylene grouphaving 2 to 6 carbon atoms, a branched alkylene group having 2 to 6carbon atoms, or a hydroxyl group-containing alkylene group having 2 to6 carbon atoms.
 11. The method of producing a polymer according to claim10, wherein the photopolymerizable polymerization precursor isrepresented by formula (2):

wherein R¹ represents an alkylene group and n is an integer of 1 to1,000.
 12. The method of producing a polymer according to claim 1,wherein the photopolymerizing step is conducted in the presence ofphotopolymerization initiator.
 13. The method of producing a polymeraccording to claim 12, wherein the photopolymerization initiator isselected from the group consisting of azo initiators and peroxideinitiators.
 14. A method of producing a polymer comprising a step ofphotopolymerizing one or more photopolymerizable polymerizationprecursors by irradiation with an activation energy ray in asupercritical fluid or in a subcritical fluid, wherein the polymer to beproduced is a film formed on an activation energy ray-transmittable basematerial which is placed so as to be exposed to the supercritical fluidor subcritical fluid.
 15. The method of producing a polymer according toclaim 14, wherein one or more photopolymerizable polymerizationprecursors are irradiated with an activation energy ray through theactivation energy ray-transmittable base material which is placed sothat a surface thereof through which the activation energy ray isincident is not exposed to the supercritical fluid or subcritical fluidand another surface thereof through which the activation energy ray isoutgoing is exposed to the supercritical fluid or subcritical fluid, tophotopolymerize the one or more polymerization precursors, whereby thepolymer film is formed on the activation energy ray outgoing surface ofthe activation energy ray-transmittable base material.
 16. The method ofproducing a polymer according to claim 15, wherein the activation energyray-transmittable base material is irradiated with the activation energyray through a mask pattern to selectively form the polymer film on anactivation energy ray-transmitted part of the activation energy rayoutgoing surface of the activation energy ray-transmittable basematerial.
 17. A method of producing a polymer comprising a step ofphotopolymerizing one or more photopolymerizable polymerizationprecursors by irradiation with an activation energy ray in asupercritical fluid or in a subcritical fluid, wherein the polymer to beproduced is a polymer containing a furry protrusion.
 18. The method ofproducing a polymer according to claim 17, wherein the height of thefurry protrusion of the polymer to be produced is 0.1 time or more asmuch as the diameter of the furry protrusion.
 19. The method ofproducing a polymer according to claim 17, wherein the height of thefurry protrusion of the polymer to be produced is 10 nm or more.
 20. Themethod of producing a polymer according to claim 17, wherein the polymercontaining the furry protrusion is formed on the activation energyray-transmittable base material which is placed so as to be exposed tothe supercritical fluid or subcritical fluid.
 21. The method ofproducing a polymer according to claim 20, wherein one or morephotopolymerizable polymerization precursors are irradiated with anactivation energy ray through the activation energy ray-transmittablebase material which is placed so that a surface thereof through whichthe activation energy ray is incident is not exposed to thesupercritical fluid or subcritical fluid and another surface thereofthrough which the activation energy ray is outgoing is exposed to thesupercritical fluid or subcritical fluid, to photopolymerize the one ormore polymerization precursors, whereby the polymer containing the furryprotrusion is formed on the activation energy ray outgoing surface ofthe activation energy ray-transmittable base material.
 22. The method ofproducing a polymer according to claim 21, wherein the activation energyray-transmittable base material is irradiated with the activation energyray through a mask pattern to selectively form the polymer containingthe furry protrusion on an activation energy ray-transmitted part of theactivation energy ray outgoing surface of the activation energyray-transmittable base material.
 23. A method of producing a polymercomprising a step of photopolymerizing one or more photopolymerizablepolymerization precursors by irradiation with an activation energy rayin a supercritical fluid or in a subcritical fluid, wherein thesupercritical fluid or subcritical fluid is supercritical carbon dioxideor subcritical carbon dioxide, wherein the photopolymerizablepolymerization precursor is photopolymerized in carbon dioxide under apressure in the range between 7 MPa and 150 MPa at a temperature in therange between 30° C. and 250° C.
 24. The method of producing a polymeraccording to claim 23, wherein the photopolymerizing step is conductedin the absence of a photopolymerization initiator.
 25. The method ofproducing a polymer according to claim 23, wherein thephotopolymerizable polymerization precursor has at least one maleimidegroup at the terminal.